The crystal structure of a lyxose-bridged dimolybdate: a redetermination of the first monosaccharide–metal complex’s structure

Allscher, Thorsten; Klüfers, Peter

doi:10.1016/j.carres.2008.12.001

Cited by 7 publications

(6 citation statements)

References 8 publications

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“…Similar phenomena have been found in reference. For instance, in the structure of the molybdenum–lyxose complex, , deprotonation occurs on three OH groups of lyxose in the complex. An observable change caused by deprotonation is that the lengths of the relevant C–O bonds (ranging from 1.413 to 1.420 Å) are lower than the C–O bonds (1.450 Å) without deprotonation.…”

Section: Resultsmentioning

confidence: 99%

“…For example, Taylor and Waters reported the single-crystal structure of molybdenum–lyxose in 1981 . Allscher and Klüfers reported the refined crystal structure of the complex in 2009 . In the complex, deprotonation was found on three OH groups of lyxose and one deprotonated OH group acted as a μ 2 -bridge and coordinated to two molybdenum ions simultaneously.…”

Section: Introductionmentioning

confidence: 99%

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Deprotonation from an OH on myo-Inositol Promoted by μ₂-Bridges with Possible Regioselectivity/Chiral Selectivity

Xie

et al. 2022

Inorg. Chem.

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Single-crystal structures of myo-inositol complexes with erbium ([Er 2 (C 6 H 11 O 6 ) 2 (H 2 O) 5 Cl 2 ]Cl 2 (H 2 O) 4 , denoted ErI hereafter) and strontium (Sr(C 6 H 12 O 6 ) 2 (H 2 O) 2 Cl2 , denoted SrI hereafter) are described. In ErI, deprotonation occurs on an OH of myo-inositol, although the complex is synthesized in an acidic solution, and the pK a values of all of the OHs in myo-inositol are larger than 12. The deprotonated OH is involved in a μ 2 -bridge. The polarization from two Er 3+ ions activates the chemically relatively inert OH and promotes deprotonation. In the stable conformation of myo-inositol, there are five equatorial OHs and one axial OH. The deprotonation occurs on the only axial OH, suggesting that the deprotonation possesses characteristics of regioselectivity/chiral selectivity. Two Er 3+ ions in the μ 2 -bridge are stabilized by five-membered rings formed by chelating Er 3+ with an O−C−C−O moiety. As revealed by the X-ray crystallography study, the absolute values of the O−C−C−O torsion angles decrease from ∼60 to ∼45°upon chelating. Since the O−C−C−O moiety is within a six-membered ring, the variation of the torsion angle may exert distortion of the chair conformation. Quantum chemistry calculation results indicate that an axial OH flanked by two equatorial OHs (double ax−eq motif) is favorable for the formation of a μ 2 -bridge, accounting for the selectivity. The double ax−eq motif may be used in a rational design of highperformance catalysts where deprotonation with high regioselectivity/chiral selectivity is carried out.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Deprotonation from an OH on myo-Inositol Promoted by μ₂-Bridges with Possible Regioselectivity/Chiral Selectivity

Xie

et al. 2022

Inorg. Chem.

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“…For example, Taylor and Waters published their pioneering work on the crystal structure of the dinuclear molybdenum–lyxose complex in 1981 . Such a structure was further refined by Allscher and Klüfers in 2009 . In the complex, three protons were removed from three OH groups of lyxose.…”

Section: Results and Discussionmentioning

confidence: 99%

“…48 Such a structure was further refined by Allscher and Klufers in 2009. 49 In the complex, three protons were removed from three OH groups of lyxose. Upon deprotonation, the lengths of the resultant C−O bonds (range from 1.413 to 1.420 Å) are lower than the C−O bond from the unaffected hydroxyl group (1.450 Å).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Unexpected Deprotonation from a Chemically Inert OH Group Promoted by Metal Ions in Lanthanide–Erythritol Complexes

et al. 2021

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Single-crystal structures of five lanthanide–erythritol complexes are reported. The analysis of the chemical compositions and scrutinization of structural features in the single-crystal data of the complexes led us to find that unexpected deprotonation occurs on the OH group of erythritol of three complexes. Considering these complexes were prepared in acidic environments, where spontaneous ionization on an OH group is suppressed, we suggest metal ions play an important role in promoting the proton transfer. To find out why the chemically inert OH is activated, the single-crystal structures of 63 rare-earth complexes containing organic ligands with multiple hydroxyl groups (OLMHs) were surveyed. The formation of μ2-bridges turns out to be directly relevant to the occurrence of deprotonation. When an OH group from an OLMH molecule participates in the formation of a μ2-bridge, the polarization ability of the metal ions becomes strong enough to promote the deprotonation on the OH group. The above structural characteristics may be useful in the rational design of catalysts that can activate the chemically inert OH group and promote the relevant chemical conversions.

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“…The investigation of the interactions between metal ions and simple sugars can improve the understanding of metal ion interactions with sugar residues of biologically important compounds and, consequently, the physiological role of metal ions, which needs to assign the binding hydroxyl or other groups, the changes of hydrogen bonds, and also to characterize the metal ion coordination of carbohydrates monitoring the ligand conformation and configuration changes forced by the complexation processes. Erythritol, galactitol, inositol, cyclohexanetriols and ribose, and so forth are often used as simple models to study the interactions between metal ions and carbohydrates. − Different ligands have various coordination modes, and one ligand may have several coordination modes: for example, galactitol may be used as two three-hydroxyl-group donor or two bidentate ligands to form a chain structure; or it may coordinate to four metal ions with its O-1 to one metal ion, O-2, -3 to the second metal ion, O-4, -5 with the third metal ion, and O-6 to the fourth metal ion to form a network structure. − Erythritol has four hydroxyl groups, and it may be used as three hydroxyl group donor or two bidentate ligands. − In this paper, new topological structures have been observed for lanthanide chloride and nitrate-erythritol complexes. Because single crystals of metal-sugar complexes are difficult to prepare, IR spectroscopy is a useful method to deduce unknown structures, so here the relationship between IR spectroscopy and structures was also discussed.…”

Section: Introductionmentioning

confidence: 99%

Interactions between Metal Ions and Carbohydrates. Spectroscopic Characterization and the Topology Coordination Behavior of Erythritol with Trivalent Lanthanide Ions

et al. 2011

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The coordination of carbohydrate to metal ions is important because it may be involved in many biochemical processes. The synthesis and characterization of several novel lanthanide-erythritol complexes (TbCl(3)·1.5C(4)H(10)O(4)·H(2)O (TbE(I)), Pr(NO(3))(3)·C(4)H(10)O(4)·2H(2)O (PrEN), Ce(NO(3))(3)·C(4)H(10)O(4)·2H(2)O (CeEN), Y(NO(3))(3)·C(4)H(10)O(4)·C(2)H(5)OH (YEN), Gd(NO(3))(3)·C(4)H(10)O(4)·C(2)H(5)OH (GdEN)) and Tb(NO(3))(3)·C(4)H(10)O(4)·C(2)H(5)OH (TbEN) are reported. The structures of these complexes in the solid state have been determined by X-ray diffraction. Erythritol is used as two bidentate ligands or as three hydroxyl group donor in these complexes. FTIR spectra indicate that two kinds of structures, with water and without water involved in the coordination sphere, were observed for lanthanide nitrate-erythritol complexes. FIR and THz spectra show the formation of metal ion-erythritol complexes. Luminescence spectra of Tb-erythritol complexes have the characteristics of the Tb ion.

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The crystal structure of a lyxose-bridged dimolybdate: a redetermination of the first monosaccharide–metal complex’s structure

Cited by 7 publications

References 8 publications

Deprotonation from an OH on myo-Inositol Promoted by μ₂-Bridges with Possible Regioselectivity/Chiral Selectivity

Deprotonation from an OH on myo-Inositol Promoted by μ₂-Bridges with Possible Regioselectivity/Chiral Selectivity

Unexpected Deprotonation from a Chemically Inert OH Group Promoted by Metal Ions in Lanthanide–Erythritol Complexes

Interactions between Metal Ions and Carbohydrates. Spectroscopic Characterization and the Topology Coordination Behavior of Erythritol with Trivalent Lanthanide Ions

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The crystal structure of a lyxose-bridged dimolybdate: a redetermination of the first monosaccharide–metal complex’s structure

Cited by 7 publications

References 8 publications

Deprotonation from an OH on myo-Inositol Promoted by μ2-Bridges with Possible Regioselectivity/Chiral Selectivity

Deprotonation from an OH on myo-Inositol Promoted by μ2-Bridges with Possible Regioselectivity/Chiral Selectivity

Unexpected Deprotonation from a Chemically Inert OH Group Promoted by Metal Ions in Lanthanide–Erythritol Complexes

Interactions between Metal Ions and Carbohydrates. Spectroscopic Characterization and the Topology Coordination Behavior of Erythritol with Trivalent Lanthanide Ions

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Deprotonation from an OH on myo-Inositol Promoted by μ₂-Bridges with Possible Regioselectivity/Chiral Selectivity

Deprotonation from an OH on myo-Inositol Promoted by μ₂-Bridges with Possible Regioselectivity/Chiral Selectivity